JP2016521644A - Sheet coated with beads - Google Patents

Abstract

Described herein is a bead-coated sheet and method for making the same, a sheet substrate selected from metal, glass and / or glass-ceramic, wherein the sheet substrate is composed of each microsphere. It includes a layer of microspheres partially embedded in the surface of the sheet substrate such that a portion projects outwardly from the surface of the sheet substrate.

Description

  The present disclosure relates to a sheet substrate comprising metal, glass ceramic and / or glass, the surface of the sheet substrate having a partially embedded layer of microspheres.

  The present disclosure relates to providing durable and / or low friction surfaces to metals, glass ceramics and / or glass substrates.

  In one embodiment, a bead coated sheet is provided, the sheet comprising a sheet substrate selected from at least one of metal, glass and glass ceramic, and a layer of microspheres, Microspheres are partially embedded in the sheet substrate surface such that some protrude outwardly from the sheet substrate surface, (a) the average diameter of the microspheres is greater than 20 micrometers, and / or Or (b) the microsphere is substantially spherical.

  In another embodiment, an article comprising a sheet coated with beads is provided, the sheet comprising a sheet substrate selected from at least one of metal, glass and glass ceramic, and a layer of microspheres, each The microspheres are partially embedded in the surface of the sheet base so that a part of the microspheres protrudes outward from the surface of the sheet base, and (a) the average diameter of the microspheres is from 20 micrometers Large and / or (b) the microspheres are substantially spherical.

  In yet another embodiment, a method of making a bead coated sheet is provided, the method comprising applying a layer of microspheres on a sheet substrate, the sheet substrate being a metal, glass, glass ceramic And embedding the microspheres in the sheet substrate surface such that a portion of each of the microspheres protrudes outwardly from the sheet substrate surface, and (a) the microspheres are selected from at least one of these combinations The average diameter of the microspheres is greater than 20 micrometers and / or (b) the microspheres are substantially spherical.

  Means for solving the above-described problems are not intended to describe each embodiment. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.

2 is a cross-sectional view of a bead coated sheet according to one embodiment of the present disclosure. FIG. 2 is a cross-sectional view of a bead coated sheet according to one embodiment of the present disclosure. FIG. 2 is a cross-sectional view of a bead coated sheet according to one embodiment of the present disclosure. FIG. 2 is a cross-sectional view of a bead coated sheet 30 in contact with a platen 38, according to one embodiment of the present disclosure. 2 is a cross-sectional view of a bead coated sheet 40 according to one embodiment of the present disclosure. FIG. 4 is an optical micrograph of Comparative Example A. 2 is an optical micrograph of Example 1. 2 is an optical micrograph of Example 1. 2 is an optical micrograph of Example 1. 2 is an optical micrograph of Example 2. 4 is an optical micrograph of Example 3. It is a figure of a friction coefficient versus normal force of Example 1 and Comparative Example D.

Definitions The following terms are used herein.
“A”, “an” and “the” are used interchangeably and mean one or more.
“And / or” is used to indicate that one or both of the described cases may occur, eg, A and / or B includes (A and B) and (A or B).

  As used herein, “glass” refers to an amorphous oxide material that exhibits a glass transition temperature, and “glass ceramic” refers to a glass that is based on a ceramic crystal of an amorphous matrix. The term “ceramic” means a crystalline inorganic material having a strong covalent bond.

  Also herein, the recitation of ranges by endpoints includes all values subsumed within that range (eg 1 to 10 includes 1.4, 1.9, 2.33, 5.. 75, 9.98, etc.).

  Also herein, the description of “at least one” includes any number of one or more (eg, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

  There is a desire to provide a durable low friction surface for more rigid substrates such as metal, glass ceramic and / or glass. For example, aluminum and stainless steel are generally known for scratching. A standard technique for improving the surface hardness of aluminum is to anodize it by growing a film of aluminum oxide on the surface via an electrochemical method. However, it is well known that anodized aluminum layers are brittle and the resistance to slip wear on the surface is not sufficient due to higher friction. An alternative is therefore desirable.

  Hard inorganic particles are dispersed in metals and metal alloys as a means of strengthening metals, and such materials are commonly referred to as metal matrix composites. For example, US Pat. No. 5,361,678 (Roopchand et al.) Discloses the addition of ceramic particles to an aluminum alloy to form a composite material, and JP-A-58-153706 (Kinouchi) Disclosed are three different methods of making composite materials comprising the reinforced particles and metal.

  In the present disclosure, improved durability (eg, scratch resistance) and / or low surface friction by partially embedding a layer of microspheres on the surface of the sheet substrate such that some microspheres protrude from the surface. It has been found that beads coated sheets with can be produced.

  Shown in FIG. 1A is one embodiment of the present disclosure. The sheet 10 coated with beads comprises microspheres 12 embedded in a sheet substrate 14.

  The substrate sheet of the present disclosure is selected from metal, glass, glass ceramic, and combinations thereof.

  Exemplary metals include aluminum, copper, tin, nickel, chromium, magnesium, titanium, iron, metal alloys (eg, stainless steel), and combinations thereof.

Glass means SiO ₂ , P ₂ O ₅ , B ₂ O ₃ , Al ₂ O ₃ , GeO ₂ , an alkali or alkaline earth modifier (eg, Na ₂ O, K ₂ O, Li ₂ O, CaO, MgO) and an amorphous material composed of a combination thereof. In one embodiment, the glass can include other components such as TiO ₂ , TeO ₂ , REO (rare earth oxide), ZnO, and the like. Representative glasses include soda lime silicate glass, borosilicate, S-glass, E-glass, titanate and aluminate-based glass.

  Glass ceramic means a polycrystalline material formed by controlled crystallization of an amorphous material. The crystallization method is a secondary heat treatment of the glass, usually under controlled heating and cooling conditions. Typical glass ceramics are lithium silicate, alkaline earth metal aluminosilicate, alkaline earth metal aluminate and rare earth aluminate.

  In one embodiment, the sheet substrate can comprise a combination of metal, glass and / or glass ceramic. For example, a glass substrate can include a thin layer of metal on its major surface, and the microspheres on the major surface of the sheet substrate are embedded in both the metal and glass material. Alternatively, the metal substrate can have a thin layer of glass or glass ceramic on its major surface, and the microspheres on the major surface of the sheet substrate are embedded in both the glass or glass ceramic and metal material.

  Since the microspheres are embedded in the sheet substrate, the sheet substrate must be thick enough to allow partial embedding of the microspheres. Generally, the sheet substrate has a thickness of at least 10, 25, 50, 100, or 250 μm (micrometers) or more (eg, at least 1 centimeter or 1 meter). There is no particular upper limit on the thickness of the sheet substrate except that it can be reasonably handled and / or can be adapted to the assembly for pressing (e.g., press gap when used).

  The microspheres are embedded in the main surface of the sheet substrate to impart beneficial properties to the surface of the sheet substrate, including, for example, improved durability and / or reduced surface friction.

  The microspheres of the present disclosure can be made from glass, ceramic, glass ceramic, metal, or combinations thereof.

  See the description above for glass, glass ceramic and metal. Ceramics include, for example, silicon oxide, aluminum oxide, tin oxide, zinc oxide, bismuth oxide, titanium oxide, zirconium oxide, lanthanoid oxide, mixtures thereof, and the like, and calcium carbonate, calcium aluminate, magnesium aluminosilicate, potassium titanate Other metal salts such as cerium orthophosphate, hydrated aluminum silicate, mixtures thereof and the like are included.

  In one embodiment, the microspheres of the present disclosure are not alumina.

  In order to produce improved surface properties, such as low friction surfaces and / or surfaces that are smooth to the touch, the microspheres must inter alia be substantially spherical and / or smooth on the surface.

  In one embodiment of the present disclosure, the microsphere is a substantially spherical particle. “Sphericality” refers to how spherical a particle is. The degree of sphericity of a particle is the ratio of the surface area of a set volume of spheres to the surface area of the same volume of particles. Substantially spherical means that the average sphericity of a plurality of microspheres is at least 0.75, 0.8, 0.85, 0.9 relative to the theoretical sphericity of 1.0 for a perfect sphere. 0.95 or 0.99.

  Roundness is another term used for the particles described and refers to the sharpness of the edges and corners of the particles. It is expressed as the ratio of the average radius of the corners to the radius of the largest inscribed circle. The relationship between sphericity and roundness can be seen with reference to the Krumbein & Sloss chart. Usually, the microspheres of the present disclosure have a high roundness, for example at least 0.6, 0.7 or 0.9.

In one embodiment, the microsphere surface of the plurality of microspheres is substantially smooth. In other words, the plurality of microspheres has an average roughness ( _Ra ) of less than 1, 0.75, 0.5, 0.25, or 0.1 micrometers. Techniques known in the art can be used to measure roughness. Usually, a stylus profiler, an optical profiler or a scanning probe microscope is used to delineate the surface and the resulting profile is used to calculate the _Ra value. Microspheres with smooth surfaces are usually made by a melting process, polishing (eg, a flame or mechanical process) and / or sintering. For example, in the melting process, beads are usually made by melting the raw material and dispersing the melt into individual droplets and then cooling. In the sol-gel method, the sol falls from the opening and the surface tension spheroidizes the sol, which is then heated and sintered.

  In the present disclosure, the microspheres of the present disclosure may be solid core microspheres or hollow core microspheres. Ideally, the microspheres must be able to withstand the applied pressure so that the integrity of the microspheres remains intact.

  The hardness of the microsphere can be selected according to the selected sheet substrate and application. In one embodiment, the hardness of the microsphere is greater than the sheet substrate. Surface hardness can be measured using Vickers hardness or other techniques known in the art. For example, soda lime silicate glass typically has a Vickers hardness of 460-500 HV, while commonly used aluminum sheet alloys (such as the 5005 series) have a Vickers hardness of 46 HV. When trying to increase the durability of the surface of the sheet substrate, it is particularly useful to have a microsphere hardness greater than the sheet substrate.

  In one embodiment of the present disclosure, the microspheres are not coated.

  In another embodiment of the present disclosure, microspheres are coated. The microspheres can be coated, for example, to improve the wettability of the microspheres and / or to make the microspheres more compatible with the sheet substrate. In one embodiment, the surface of the microsphere includes at least one of a metal, a metal oxide, a flux, a wettable layer, and combinations thereof.

  In one embodiment of the present disclosure, the microspheres are preferably free of defects. As used herein, the phrase “defect free” means that the microspheres have a small amount of undesirable bubbles and / or a small amount of foreign matter.

  Microspheres are usually sized with a screen sieve to provide an effective distribution of particle sizes. Sifting is also used to characterize the microsphere size. For sieving, using a series of screens with controlled size openings, the microspheres passing through the openings are considered equal to or smaller than the size of the openings. For microspheres, this is accurate because the microsphere's cross-sectional diameter is almost always the same regardless of the orientation of the screen opening. In order to control economy and maximize surface microsphere packing, it is desirable to use the widest possible dimension range. However, depending on the application, it may be necessary to limit the microsphere size range to provide a more uniform microsphere application surface.

  In some embodiments, a useful range of volume-based microsphere average diameter is at least 5, 10, 20, 25, 30, 35, 40, 50, 75, 100, 150, 200 or 250 μm, with a maximum 500, 600, 800, 900 or 1000 μm. The microspheres can have a unimodal or multimodal (eg, bimodal) particle size distribution depending on the application.

  Microspheres useful in the present disclosure may be transparent, translucent (partially transparent) or opaque. In one embodiment, the microsphere has an average refractive index of at least 1.4, 1.6, 1.8, 2.0, 2.2 or 2.6.

  In this disclosure, the microspheres are embedded enough to create sufficient adhesion between the sheet substrate and the microspheres (so that the microspheres do not easily peel off the surface), while achieving a friction reducing effect The microspheres are partially embedded on the surface of the sheet substrate so that they are not embedded to a lesser extent. Typically this is because at least 15, 20, 30, 40 or 50% of the average diameter of each microsphere is embedded in the sheet substrate, and up to 70, 80, 85 or 90% of the average diameter of each microsphere. It means to be embedded in a sheet substrate.

  Less than or equal to a single layer of microspheres (ie, one layer of microspheres) is used for the sheet substrate surface.

  In one embodiment, to create a uniform monolayer, liquid is applied to the surface of the sheet substrate and then microspheres are applied to the surface, or the microspheres are mixed with the liquid to form a dispersion; It is applied to the surface of the sheet substrate. The liquid makes it possible to disperse the microspheres and form a monolayer on the surface of the sheet substrate. The thin liquid layer helps maintain a bead layer that is uniformly intimately packed in place during sample transfer to the press and can be removed cleanly when exposed to temperature. The liquid must disperse the microspheres on the surface of the sheet substrate and not evaporate, and such liquid contains a solvent or binder.

  Usually, the solvent is selected so that it does not evaporate while the microsphere monolayer is formed on the sheet substrate, but is removed during and / or after the microsphere embedding. Representative solvents include triglycerides (eg, oleic acid) and diols and polyols (eg, glycerol and glycol). In one embodiment, it is desirable that the solvent does not leave any residue on the resulting bead-coated sheet.

  Typically, in a bead-coated sheet, a monolayer of microspheres is achieved using an adhesive or tacky material that holds the beads. When exposed to high temperatures, these sticky materials burn and leave an undesirable dark residue. When using the cold bead sinking method, the adhesive binder material remains in the procedure and can potentially affect the mechanical properties and adhesion to the support sheet.

  Despite the binding agent can be used in one embodiment of the present disclosure, the bead-coated sheet microspheres are embedded in the sheet substrate. In other words, the underlying sheet substrate has surface characteristics that are recessed by microspheres.

  In some embodiments, the liquid used to form the microsphere monolayer is removed during or after filling the microspheres. Removal is usually by heating to a temperature that causes evaporation or decomposition of the liquid. A liquid residue may or may not remain.

  In another embodiment, a uniform monolayer of microspheres is created by using a screen or patterned tray. In this embodiment, a screen or tray is placed on top of the sheet substrate to dispense a large amount of microspheres onto the substrate to create a bead monolayer to remove excess, then the beads to the substrate Press on.

  FIG. 1B shows another embodiment of a bead coated sheet 10 that includes microspheres 12 embedded in a sheet substrate 14. The bead-coated sheet microsphere monolayer is ideally close packed so that the gaps between individual microspheres are less than 5, 4, 2 or 1 times the average microsphere diameter. Has been. However, depending on the particle size distribution of the microspheres and the method of applying it to the surface of the sheet substrate, some less than the closest packed state can occur. In order to obtain the beneficial properties of partially embedded microspheres, usually at least 50, 60, 70, 80, 90 or 95% of the bead-coated sheet surface is coated with a microsphere monolayer.

  In the present disclosure, the microspheres are at least partially embedded in the surface of the sheet substrate such that a portion of each microsphere projects outwardly from the surface of the sheet, and the microspheres are on the underlying sheet base. Indent the material. In the present disclosure, the microspheres are sufficiently embedded in the surface of the sheet substrate so that they are not easily removed from the surface of the sheet substrate.

  The microspheres of the present disclosure are embedded in a sheet substrate using pressure and optionally heat. In one embodiment, a plurality of microspheres are placed on a sheet substrate, a platen or other smooth (eg, flat) surface is placed on the microsphere layer, pressure is applied, and the microspheres The sphere is pushed into the sheet substrate. In another embodiment, the substrate sheet may be placed on the plurality of microspheres with any weight placed on the substrate sheet, and gravity (or additional pressure) may be applied to the plurality of microspheres. It may be used for embedding in a substrate sheet. Although pressing can be used alone, heat is usually used to soften the sheet substrate to facilitate the embedding process.

  Depending on the substrate sheet and microspheres selected and whether heated or not, forces in the range of at least 1, 5, 10 or 20 kN may be used and up to 50, 100, 200 or 500 kN can be used. Cold pressure uses pressure so that the substrate material exceeds (or is close to) its yield point without heating. In one embodiment, the pressure is at least in the range of 20, 40, 60, 80, 100 or 125 MPa and may be used at a maximum of 200, 225, 250, 275, 300 or 350 MPa.

Heat can be applied to soften the sheet substrate to facilitate the embedding process. Commonly used temperatures are usually within a few degrees of the softening or melting temperature of the substrate. As used herein, melting temperature refers to both the melting temperature of materials such as metals, T _m , and the glass softening temperature of glass. Typically for metals, the temperature is at least 60, 70, 80 or 90% of the melting temperature of the substrate. Typically, for glass and glass ceramic substrates, the temperature is at least 60, 70, 80, 90, 95, 99% of the Littleton softening temperature of the substrate. When hot pressing a metal substrate, it may be advantageous to perform the embedding process in a non-oxidizing environment to facilitate adhesion of the microspheres to the substrate.

  The combination of microsphere and sheet substrate material is selected such that the microsphere has a higher melting temperature than the sheet substrate. In one embodiment, the melting temperature of the microspheres is 10, 25, 50, 100 or 150 ° C. higher than the melting temperature of the sheet substrate. By selecting such a combination, a durable coating on the sheet substrate can be provided.

  In one embodiment, the melting temperature of the microspheres is approximately close to the melting temperature of the sheet substrate. As a result, as shown in FIG. 2, the microspheres are connected by a thin connecting portion, the microspheres 22 of the sheet 20 coated with beads are partially melted or softened, and the microspheres are bonded to each other. The connection part 26 between the microspheres to be formed is formed. However, in the present disclosure, the microspheres embedded in the sheet substrate remain some angular curved. Without being bound by theory, it is believed that this angular curvature provides the low friction properties of the bead-coated substrate surface.

  In one embodiment, it may be important that the hand has a smooth surface. In particular, this can be achieved by ensuring that the height difference of the vertices of each embedded microsphere is in the range of 5, 7, 10, 12, 15 or 20 micrometers. Referring to FIG. 4 showing the microspheres 42 and 43 embedded in the sheet substrate 44, “d” represents the difference in height between the vertices of the microspheres 42 and 43. The smaller the difference in the height of the microsphere vertices, the smoother the surface feel.

  The difference in peak height can be minimized using a platen that applies pressure to the microspheres to facilitate embedding in the sheet substrate. The platen must be stiff and smooth (eg, flat) so that the uniform pressure applied to the sheet substrate also allows sinking. Because the platen applies pressure, a large distribution of microsphere sizes can be used in the present disclosure and a smooth low friction surface can also be achieved. Shown in FIG. 3 is a platen 36 on microspheres 32 and 33 of different sizes embedded.

  The sheet substrate need not be flat, but the sheet substrate usually has a substantially flat surface to facilitate the implantation of the microspheres. The sheet substrate can have a curved or non-linear characteristic, which matches the characteristics of the platen (or pressure plate). Further, depending on the application, the resulting bead-coated sheet can then be formed into a non-planar object.

  An advantage of performing the methods described herein is that, in one embodiment, the resulting bead-coated sheet substantially comprises a binder layer between the microsphere layer and the sheet substrate. It is not. This can be advantageous when low friction metal surfaces are used in high temperature applications, which can be advantageous, for example, in automotive gas turbine operations.

  The bead-coated sheet of the present disclosure has a durable low friction and / or smooth surface.

  In one embodiment, the resulting surface of the bead coated sheet has a higher pencil hardness than the sheet substrate as measured by a pencil hardness test. Surface durability can be measured with pencil hardness. Such techniques are known in the art. Usually, pencils of various hardnesses (high hardness to low hardness) are moved along the material surface, and the surface is visually inspected for scratches, breakage, and the like. The stiffest level of pencil that does not scratch, break or remove surface microspheres is reported as the pencil hardness of the film.

  In one embodiment, the resulting surface of the bead coated sheet has a friction less than 0.6, 0.5, 0.4, 0.3 or 0.2 when tested with the tactile friction test method (below). Has a coefficient.

  In one embodiment, the resulting surface of the bead-coated sheet has a coefficient of friction of less than 0.5, 0.4, 0.3, 0.2 or 0.1 when tested with a tribometer. In one embodiment, the resulting surface of the bead-coated sheet is 0.5, 0.4, 0.3, 0.2 or 0 when tested in a 100 cycle and 1 N load friction test method (below). Have a coefficient of friction of less than 1.

  Durable low friction surfaces are generally desired in a wide variety of consumer and industrial applications such as industrial, consumer or medical devices and components. Sheets coated with the beads of the present disclosure can be applied to durable cases of electronic devices, road marking coating materials, low friction correction materials, low noise stethoscopes, and high friction and low friction and good resistance. It can be used as a machine part that requires wear.

A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below.
Embodiment 1. FIG. A sheet coated with beads, the sheet comprising a sheet substrate selected from at least one of metal, glass, and glass ceramic, and a layer of microspheres, a portion of each microsphere being external Microspheres are partially embedded in the surface of the sheet substrate so as to protrude from the surface of the sheet substrate in a direction, (a) the average diameter of the microspheres is greater than 20 micrometers, and (b) the A sheet wherein the microspheres are substantially spherical, or (c) the average diameter of the microspheres is greater than 20 micrometers and the microspheres are substantially spherical.

  Embodiment 2. FIG. The bead-coated sheet of embodiment 1, wherein the surface of the bead-coated sheet has a coefficient of friction of less than 0.4.

  Embodiment 3. FIG. The bead-coated sheet of embodiment 1, wherein the apex of each microsphere embedded in the surface of the sheet substrate has a height difference of less than 20 micrometers.

  Embodiment 4 FIG. The bead-coated sheet according to any one of embodiments 1-3, wherein the bead-coated sheet is substantially free of a binder layer between the microsphere layer and the sheet substrate.

  Embodiment 5. FIG. The bead-coated sheet according to any one of Embodiments 1 to 4, wherein the microsphere layer is equivalent to or less than a single layer of microspheres.

  Embodiment 6. FIG. Embodiment 6. The bead-coated sheet of any one of embodiments 1-5, wherein the sheet substrate has a thickness of at least 10 micrometers.

  Embodiment 7. FIG. Embodiment 7. The bead-coated sheet of any one of embodiments 1-6, wherein the microsphere surface comprises at least one of a metal, metal oxide, flux, wettable layer, and combinations thereof.

  Embodiment 8. FIG. Embodiment 8. The bead-coated sheet of any one of embodiments 1-7, wherein the microspheres have an average diameter of 25-1000 micrometers.

  Embodiment 9. FIG. Embodiment 9. The sheet coated with beads according to any one of embodiments 1-8, wherein the microspheres are selected from the group consisting of glass, ceramic, glass ceramic, metal and combinations thereof.

  Embodiment 10 FIG. Embodiment 10. The sheet coated with beads according to any one of embodiments 1-9, wherein the microspheres are transparent, translucent or opaque.

  Embodiment 11. FIG. In any one of Embodiments 1-10, wherein the metal is selected from the group consisting of aluminum, copper, tin, nickel, chromium, magnesium, titanium, iron and their alloys and combinations thereof, and stainless steel. Sheet coated with the described beads.

  Embodiment 12 FIG. The bead-coated sheet of any one of embodiments 1-11, wherein 20-90% of the average diameter of each microsphere is embedded in a sheet substrate.

  Embodiment 13 FIG. The sheet | seat coated with the bead as described in any one of Embodiments 1-12 with which the said microsphere is connected with the thin connection part.

  Embodiment 14 FIG. The sheet coated with beads according to any one of embodiments 1 to 13, wherein the melting temperature of the microspheres is higher than the melting temperature of the sheet substrate.

  Embodiment 15. FIG. Embodiment 15. The bead-coated sheet of any one of embodiments 1-14, wherein 90% of the sheet substrate surface is coated with microspheres.

  Embodiment 16. FIG. 16. An article comprising a sheet coated with the beads of any one of embodiments 1-15.

  Embodiment 17. FIG. A method of making a bead-coated sheet, comprising providing microspheres, (a) an average diameter of the microspheres is greater than 20 micrometers, and (b) the microspheres are substantially spherical, or (C) the average diameter of the microspheres is greater than 20 micrometers and the microspheres are substantially spherical; applying a layer of microspheres on the sheet substrate; and the sheet substrate is metal, glass Embedded in the surface of the sheet substrate so that a portion of each of the microspheres protrudes outward from the surface of the sheet substrate, selected from the group consisting of glass ceramics and combinations thereof; A method for producing a bead-coated sheet.

  Embodiment 18. FIG. Embodiment 18. The method of embodiment 17, wherein the surface of the bead coated sheet has a coefficient of friction of less than 0.4.

  Embodiment 19. FIG. Embodiment 19. The method of embodiment 17 or 18, wherein heat and / or pressure is used to embed microspheres on the surface of the sheet substrate.

  Embodiment 20. FIG. Embodiment 20. The method of embodiment 19 wherein the platen is used to embed microspheres on the surface of the sheet substrate.

  Embodiment 21. FIG. Embodiment 21. The method of any one of embodiments 17-20, wherein the microspheres are selected from the group consisting of glass, ceramic, glass ceramic, metal, and combinations thereof.

  Embodiment 22. FIG. Embodiment 22. The method of any one of embodiments 17-21, wherein the liquid is applied to the surface of the sheet substrate prior to application to the microsphere layer.

  Embodiment 23. FIG. Embodiment 23. The method according to any one of embodiments 17-22, wherein the microspheres are applied to the sheet substrate surface as a mixture comprising microspheres and a liquid.

  Embodiment 24. FIG. 24. The method of embodiment 22 or 23, further comprising removing the liquid during or after embedding the microspheres in a sheet substrate surface.

  Embodiment 25. FIG. Embodiment 25. A method according to any one of embodiments 22-24, wherein the liquid is a solvent or a binder.

  Embodiment 26. FIG. Embodiment 26. The method of embodiment 25, wherein the solvent is oleic acid.

  Embodiment 27. FIG. Embodiment 16. The embodiment of any one of embodiments 1-15, wherein the bead-coated sheet surface has a coefficient of friction of less than 0.4 when measured using a 100 cycle and 1 N load friction test method. Sheet coated with beads.

  Embodiment 28. FIG. The sheet | seat coated with the bead as described in any one of Embodiment 1-15 and Embodiment 27 whose pencil hardness of the obtained material has pencil hardness higher than the said sheet | seat base material when it measures by a pencil hardness test.

  Embodiment 29. FIG. The bead coated sheet of any one of embodiments 1-15 and 27 or 28, wherein the surface of the bead coated sheet has a coefficient of friction of less than 0.5 as measured by a tactile friction test method. Sheet.

  The advantages and embodiments of the present disclosure are further illustrated by the following examples, although the specific materials and their amounts listed in these examples, as well as other conditions and details, should unduly limit the present invention. Should not be interpreted. In these examples, all percentages, ratios and ratios are by weight unless otherwise indicated.

  Unless otherwise specified or specified, all materials are commercially available, eg, from Sigma-Aldrich Chemical Company (Milwaukee, Wis.) Or are known to those skilled in the art.

  In the examples below, these abbreviations are used: cm = centimeter, μm = micrometer, kN = kilonewton, sec = second, and N = newton.

Test Method Prior to testing, the samples were wiped with isopropanol.

Friction Test A tribometer (standard tribometer (obtained from CSM Instruments, Needham, Mass., USA)) with a stainless steel ball as a static partner was used. The sample passed back and forth under a preset applied load and a steel ball with a stroke length of 0.4 cm at a speed varying between 0.05 cm / sec and 0.4 cm / sec (one cycle is forward Followed by a reverse). The lateral force of the stainless steel ball was monitored and recorded by a tribometer for conversion to the coefficient of friction (COF). The applied load and the number of cycles were varied and the samples were visually inspected under an optical microscope after the test. COF was measured by dividing the lateral force of the steel ball under test by the applied normal force.

Tactile Friction Test ForceBoard (manufactured by Industrial Dynamics Sweden AB) was used to measure tactile friction. This system uses multiple strain gauges to record the normal and lateral forces applied to the sample.

  The coefficient of dynamic friction (COF) is a unitless coefficient associated with a normal force (in this case, with a finger) applied to the lateral or frictional force of a finger when dragged along a surface. The method used to test the COF in the haptic friction test will be described later. Since skin surface friction is highly dependent on the degree of skin hydration, it is important to compare COF values between samples under conditions where skin hydration is consistent. The following method therefore includes steps to ensure uniform hydration of the skin.

  A specimen of the material to be tested was affixed to the surface of the force plate using a repositionable adhesive.

  The subject's hands were washed using a neutral detergent to remove any surface oil and then dried using a paper towel. The subject's left index finger is then immersed in a small amount of deionized water, sufficient to wrap the area of the finger in contact with the surface of the specimen. After soaking for 20 seconds, the fingers are removed from the water and the surface moisture is then dried using an absorbent paper towel.

  The subject's left index finger (at an angle of approximately 30 degrees from vertical) then increases the force as the finger moves along the surface, with the surface of the specimen in the normal force range of approximately 0.5 to 10 Newtons. Was dragged along. After each finger movement, it was immersed in water and dried as described above. For vertical and lateral force data recorded with each movement, the process of dragging the entire surface with a finger, dipping and wiping the finger was repeated about 4-6 times for each sample.

  The force data was then converted to COF data and a range of COF values for various normal forces was plotted. Multiple movements of each sample were plotted simultaneously to serve as a data integrity check.

Pencil Hardness Method The sample surface was evaluated for pencil hardness after a similar procedure disclosed in ASTM D3363-05 (2011) e2 “Standard Test Method for Film Hardness by Pencil Test”. Abrasive paper (particle size 400) was attached to a flat and smooth bench top with double-sided tape. A pencil lead (Totiens drawing lead with a mechanical lead holder) was worn against the abrasive paper at an angle of 90 ° until there was no chipping or scratches on the tip and a flat and smooth circular cross section was made. The force at the pencil tip was fixed at 7.5 N or in some cases less. A self-supporting bead membrane was placed on the glass surface. By using a newly prepared pencil lead for each test, an Elcomator 3086 Motorized Pencil Hardness Tester (obtained from Elcomtor Incorporated (Rochester Hills, MI)) using a 45 ° angle to the film and Pressed firmly with the desired load (7.5 N), a line of at least 1/4 inch (0.64 centimeters) in length was drawn “forward” across the test panel. Three pencil marks were made for each grade of core hardness. Prior to inspection, the crushed wick was removed from the test area using a paper towel moistened with isopropyl alcohol. The film was inspected visually for defects and the first 1/8 to 1/4 inch (0.318 to 0.64 centimeter) of each pencil mark with an optical microscope (50 to 1000 magnification). The method comprises a hardness tester, transitioning from a stiffer core to a softer core until a pencil was found that did not scratch or tear the film, or that could not be removed or partially removed. Repeated. At least two of the three traces of hardness of each core required that these criteria be met for passage. The stiffest level of core passed through was reported as the pencil hardness of the film.

Comparative Example A
Aluminum plate (5 cm × 5 cm × 3 mm (2 inches × 2 inches × 3 mm), obtained from Lawrence and Frederick Inc., 5005 alloy, hardness H34).

Example 1
An aluminum plate (5 cm × 5 cm × 3 mm (2 inches × 2 inches × 3 mm)) was wiped with oleic acid and the excess was wiped away leaving a thin layer of oleic acid on the surface of the aluminum plate. Then glass beads (soda lime silicate, diameter size 40-60 μm, roundness 96-98%, obtained from Swarco Industries (Columbia TN)) are flood coated onto the oleic acid coated surface and the excess beads are tapped. It was dropped.

  Next, an aluminum plate containing glass microspheres was placed between two flat 2.5 inch (6.4 centimeter) diameter tungsten carbide discs to make Toshiba Machine (Japan Oka 2068- Numazu, 410-8510, Shizuoka Prefecture, Japan). 3) Mounted on an improved hot press made by The chamber was filled with nitrogen to remove oxygen and an infrared lamp was used to heat the material. Pressure was applied during heating. When the pressure reached 645 ° C., a force of 10 kN was applied and the displacement of the crosshead was monitored to control the degree of bead subsidence. Once the desired crosshead movement was obtained, the run was terminated and the sample was rapidly cooled to 50 ° C. with flowing nitrogen. The sample was then removed from the press.

  The obtained sample had a surface that was silky smooth and matte in appearance. Microscopic images confirmed the presence of microspheres that were pressed into the substrate and packed tightly. The image shows that the glass beads melt and coalesce slightly during pressing as the processing temperature approaches the melting temperature of the glass.

(Example 2)
An aluminum plate (5 cm × 5 cm × 3 mm) was wiped with oleic acid and the excess was wiped away leaving a thin layer of oleic acid on the surface of the aluminum plate. Glass ceramic beads (made in the melting process according to the disclosure of 25-40 μm in diameter, refractive index 2.42, US Pat. No. 7,947,616 (Frey et al., Example 8)) are then applied to the oleic acid coated surface The excess beads were lightly tapped and flooded.

  An aluminum plate containing glass ceramic microspheres was then placed between two flat 2.5 inch (6.4 centimeter) diameter tungsten carbide discs and placed on a modified Toshiba machine hot press. The chamber was filled with nitrogen to remove oxygen and an infrared lamp was used to heat the material. When the pressure reached 645 ° C., a force of 10 kN was applied and the displacement of the crosshead was monitored to control the degree of bead subsidence. Once the desired crosshead movement was obtained, the run was terminated and the sample was rapidly cooled to 50 ° C. The sample was then removed from the press.

  The obtained sample had a surface that was silky smooth and matte in appearance. Microscopic images confirmed the presence of microspheres that were pressed into the substrate and packed tightly. The image shows no apparent melting / coalescence of the glass ceramic beads during processing.

  Comparative Example A and Examples 1-2 were tested using the friction test and pencil hardness method described above. The results are shown in Table 1.

  FIG. 5A is an optical micrograph of the surface of Comparative Example A after performing a friction test with an applied load of 1 N and 100 cycles. FIG. 5B is an optical micrograph of the surface of Example 1 before the friction test. FIG. 5C is an optical micrograph of the surface of Example 1 after performing a friction test at an applied load of 1 N and 1000 cycles. FIG. 5D is an optical micrograph of the surface of Example 1 after performing a 6H pencil hardness test. FIG. 5E is an optical micrograph of the surface of Example 2 after performing a friction test at an applied load of 1 N and 800 cycles.

Example 3
An aluminum plate (5 cm × 5 cm × 3 mm) was wiped with oleic acid and the excess was wiped away leaving a thin layer of oleic acid on the surface of the aluminum plate. Glass beads (soda lime silicate, diameter 40-60 μm, roundness 96-98%, obtained from Swarco Industries) were flood coated onto the oleic acid coated surface and excess beads were tapped off.

  The aluminum plate containing the microspheres was then placed in a hydraulic uniaxial press (available from Carver, Inc. (Summitt, NJ)) fitted with a 3.81 cm stainless steel die. A WC plate was placed under the aluminum substrate to prevent bending of the sample and a load of 35.59 kN was applied. The surface of the sheet in which the beads were embedded was pressed and then observed under a microscope. FIG. 6 is an optical micrograph of the surface of Example 3. The beads were embedded in the metal surface with as much as 50% bead sinking and the sample had a silky smooth feel.

Comparative Example B
Tin plate substrate (5 cm × 5 cm × 3 mm) obtained from McMaster Carr Industries (Elmhurst IL).

Example 4
The tinplate substrate used in Comparative Example B was prepared using glass beads (soda lime silicate, diameter dimensions 40-60 μm, roundness 96 using the preparation and pressing procedure described in Example 3. -98%, obtained from Swarco Industries (Columbia TN)), using a single screw Carver press and 57.8 kN pressure.

Comparative Example C
Copper plate base material (5 cm × 5 cm × 3 mm) obtained from McMaster Carr.

(Example 5)
The copper plate used in Comparative Example C was wiped with oleic acid and the excess was wiped away leaving a thin layer of oleic acid on the surface of the copper plate. Then the glass ceramic beads _{(La 2 O} 3 45 _wt%, AI _{2 O} 3 20 wt%, _ZrO 2 30 wt% and an average diameter of 38 to 75 micrometers first following U.S. patents 7,563 containing TiO ₂ 5 wt% No. 293 (made as disclosed in Rosenflanz) was flood coated onto the oleic acid coated surface and excess beads were tapped off.

  A copper plate containing glass ceramic microspheres was then placed between two flat 2.5 inch (6.4 centimeter) diameter tungsten carbide discs and placed on a modified Toshiba Machine hot press. The chamber was filled with nitrogen to remove oxygen and an infrared lamp was used to heat the material. Pressure was applied during heating. When the pressure reached 800 ° C., a force of 50 kN was applied for 15 minutes. Once the desired crosshead movement was obtained, the run was terminated and the sample was rapidly cooled to 50 ° C. with flowing nitrogen. The sample was then removed from the press.

  Comparative Examples B and C and Examples 4 and 5 were tested using a friction test. The results are shown in Table 2.

Comparative Example D
The aluminum plate substrate used in Comparative Example A was E-glass using the preparation and pressing procedure described in Example 1 except that the particles were pressed at 650 ° C. for 15 minutes at 98 kN pressure. Pressed with powder particles (irregularly shaped particles (200-400 mesh) made by Vitro Minerals (Conyers, GA)). The pressed sample showed a rough feel that was very different from the sample with the indented microsphere beads.

  Example 1 and Comparative Example D were tested using haptic friction. The above test and results are shown in FIG. The measured value shows that the glass powder particles pressed into the aluminum substrate have a higher COF compared to Example 1 using substantially round microspheres.

Example 6 and Comparative Example E
Soda lime silicate glass plate (6 cm × 4 cm × 5 mm) is a glass ceramic bead (diameter 20-80 μm, refractive index 2.42, US Pat. No. 7,947,616 (Frey et al., Placed on the deposit)) produced by the melting process according to the disclosure of Example 8). An alumina crucible containing glass ceramic microspheres and a soda lime glass plate placed on top of the microspheres is then placed in a furnace and heated to 800 ° C. at a heating rate of 10 ° C./min and then at 800 ° C. for 30 minutes. Isothermal treatment.

  The furnace was cooled and the glass plate was removed from the furnace. It was observed that the glass ceramic beads were embedded in the glass plate on the side in direct contact with the beads. The other side of the board remained unbeaded.

  The bead side of the soda lime silicate board (Example 6) and the beadless back side of the board (Comparative Example E) were tested using a friction test. The results are shown in Table 3.

  It will be apparent to those skilled in the art that predictable modifications and variations of the present invention can be made without departing from the scope and spirit of the invention. The present invention should not be limited to the embodiments described in this application for purposes of illustration.

Claims (11)

A sheet coated with beads, the sheet comprising:
A sheet substrate selected from at least one of metal, glass and / or glass ceramic;
A microsphere layer, and the microspheres are partially embedded in the sheet base material surface such that a part of each microsphere projects outward from the sheet base material surface; A bead-coated sheet in which the average diameter of the spheres is greater than 20 micrometers and / or (b) the microspheres are substantially spherical.   The bead-coated sheet of claim 1, wherein the surface of the bead-coated sheet has a coefficient of friction of less than 0.4 as measured using a 100 cycle and 1 N load friction test method.   The sheet | seat coated with the bead of Claim 1 or 2 which has pencil hardness higher than the said sheet | seat base material when the pencil hardness of the obtained material is measured by a pencil hardness test.   The bead-coated sheet of claim 1, wherein the surface of the bead-coated sheet has a coefficient of friction of less than 0.5 as measured using a tactile friction test method.   The bead-coated sheet according to claim 1, wherein the apex of each of the microspheres embedded in the sheet substrate surface has a height difference of less than 20 micrometers.   6. The bead-coated sheet according to any one of claims 1 to 5, wherein the bead-coated sheet is substantially free of a binder layer between the microsphere layer and the sheet substrate.   The sheet coated with beads according to any one of claims 1 to 6, wherein the microspheres are connected by a thin connecting portion.   An article comprising a sheet coated with the beads according to any one of claims 1-7. A method for producing a sheet coated with beads,
Providing a microsphere; (a) the average diameter of the microsphere is greater than 20 micrometers; and / or (b) the microsphere is substantially spherical;
Applying a layer of microspheres on the sheet substrate, the sheet substrate being selected from the group consisting of metal, glass, glass ceramic and combinations thereof, and a portion of each of the microspheres facing outward And embedding microspheres on the surface of the sheet base material so as to protrude from the surface of the sheet base material.   The method according to claim 9, wherein the microspheres are embedded in the surface of the sheet substrate using a platen.   11. A method according to claim 9 or 10, wherein the liquid is applied to the surface of the sheet substrate before being applied to the microsphere layer and the liquid is oleic acid.

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